Facile Self‐Assembly Synthesis and Characterization of Diselenophosphinato Octanuclear Cu<sup>I</sup> Clusters Inscribed in a Twelve‐Vertex Selenium Polyhedron

Liao, P. K.; Shi, De-Ren; Liao, Jian‐Hong; Liu, C. W.; Artem’ev, Alexander V.; Kuimov, Vladimir A.; Гусарова, Н. К.; Трофимов, Б. А.

doi:10.1002/ejic.201200593

Cited by 30 publications

(11 citation statements)

References 32 publications

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“…Various dithiophosphinato or diselenophosphinato complexes have been synthesized, with the general structures of M(EEPR 2 ) n , where M = metal ions of Group IIIA (trivalent), IIB (divalent), IVA (divalent), and IB (monovalent), and R = alkyl, phenyl, and alkoxy groups. [28][29][30][31][32] Some of these complexes have been used in SSPAs to make E-based binary semiconductor NCs and thin films but only at temperature higher than 300 8C. [9][10][11][12][13][14] To explore the common mechanism for the formation of the various ME semiconductor nanomaterials from the SSPA and DSPA, herein, CdSe was investigated as a model system in detail.…”

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The Formation Mechanism of Binary Semiconductor Nanomaterials: Shared by Single‐Source and Dual‐Source Precursor Approaches

Yu¹,

Li²,

Zeng³

et al. 2013

Angewandte Chemie

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Both singlesource and dual-source precursor approaches (SSPA and DSPA) to binary semiconductors have been documented. [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] Such materials consist of elements from two groups such as IIB and VIA. The single-source precursors (SSPs) consist of the metallic and nonmetallic elements of the semiconductor constituents in a single molecule. [9][10][11][12][13][14] DSPA uses separated metallic-element and nonmetallic-element precursors, which commonly involve metal carboxylates (M(OOCR) n such as M = Zn, Cd, Pb, Cu, In) and phosphine chalcogenides (such as E = PHR 2 where E = S, Se, Te), [15][16][17][18][19][20][21][22][23][24][25][26][27] respectively. Despite the large number of recipes developed for the various colloidal semiconductor nanocrystals (NCs) in the past 20 years, there is still little understanding of their formation mechanisms. To realize the full potential of semiconductor materials, there is an urgent need to advance our mechanistic understanding. Filling this gap in our knowledge should have practical implications such as lowering the high temperature currently employed for syntheses and offering new avenues to optimize the design of low-temperature approaches to novel semiconductor nanomaterials.Recent evidence suggests that the formation of various binary semiconductor NCs by SSPAs and DSPAs may share analogous mechanisms. A DSPA to CdS quantumm dots (QDs) at 160 8C in tetradecane (CH 3 (CH 2 ) 12 CH 3 ) was reported from the reaction of cadmium stearate (Cd(OOCC 17 H 35 ) 2 ) and diphenylphosphine sulfide (S= PHPh 2 ). [25] DSAPs to E-based semiconductor QDs have become popular with metal carboxylates as cation precursors and diphenylphosphine chalcogenides E = PHPh 2 as anion precursors. [15][16][17][18][19][20][21][22][23][24][25][26][27] Astonishingly, the lack of a common formation mechanism is actually accompanied by the same 31 P NMR identification of RCOO-PPh 2 (R = C 17 H 33 99 ppm (3 in Scheme 1) or C 6 H 5 102 ppm) and Ph 2 P-PPh 2 (À14 ppm, 4) for the various DSPAs to PbSe, [18] CdSe, [19][20][21][22] ZnSe, [23,24] ZnS, [24] and ZnSeS, [24] together with C 17 H 33 COO-P(Se)Ph 2 (77 ppm, 5) for the Se-based NCs. [18,[21][22][23][24] Furthermore, the conversion of Se = PHPh 2 to diphenyldiselenophosphinate derivatives (ÀSeSePPh 2 ) has been documented. [18,19,22] For instance, [22] the formation of RCOOCdSeSePPh 2 (c) was proposed from a Cd(OA) 2 + Se=PHPh 2 reaction after the release of oleic acid (C 17 H 33 COOH or RCOOH, R = C 17 H 33 ) from (RCOO) 2 Cd(Se = PHPh 2 ) 2 (b) followed by diphenylphosphine (HPPh 2 or DPP) from RCOOCd(Se À PPh 2 )-(Se = PHPh 2 ) (d) through cleavage of the Se = P bond of the Se=PHPh 2 coordination arm.

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The Formation Mechanism of Binary Semiconductor Nanomaterials: Shared by Single‐Source and Dual‐Source Precursor Approaches

Yu¹,

Li²,

Zeng³

et al. 2013

Angewandte Chemie

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“…10 Along this line, a group of metal complexes including alkali and d-block elements passivated by a number of selenium containing ligands, namely, diselenophosphates (dsep), diselenophosphonates (dsepo), diselenophosphinates (dsepi), and triselenophosphonates (tsepo) have been established to be useful sources in metal selenide nanomaterial synthesis. 2a Discrete group 11 metals (Cu I , Ag I , and Au I ) with diselenophosph(in)ates ligands [14][15][16][17][18] are primarily studied by the Liu and O'Brien groups. 19 Anion-centered multinuclear Cu I and Ag I clusters of this kind are particularly interesting due to their intrinsic characteristics, reminiscent of guest-host supramolecules.…”

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confidence: 99%

“…13 For example, by taking advantage of the labile P-Se bond, diselenophosphates-stabilized tetrahedral copper cluster [Cu 4 {Se 2 P(O i Pr) 2 } 4 ] was employed as a single source precursor for the fabrication of Cu 2-x Se nanowires with lengths of several micrometers and diameters of 30-50 nm via CVD process. 2a Discrete group 11 metals (Cu I , Ag I , and Au I ) with diselenophosph(in)ates ligands [14][15][16][17][18] are primarily studied by the Liu and O ' Brien groups. 2a Discrete group 11 metals (Cu I , Ag I , and Au I ) with diselenophosph(in)ates ligands [14][15][16][17][18] are primarily studied by the Liu and O ' Brien groups.…”

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confidence: 99%

“…Unlike an empty [Cu 8 {Se 2 P(CH 2 CH 2 Ph) 2 } 6 ] 2+ cubic complex, which can be easily isolated and subsequently converted into [Cu 8 (X){Se 2 P(CH 2 CH 2 Ph) 2 } 6 ](PF 6 ) (X = H -, Cl -, Br -) in the presence of anion sources,18 the synthesis of analogous, empty cubic complex failed in the presence of diselenocarbamate ligands under similar circumstances. Cluster 1 is very air-sensitive and prevented both satisfactory elemental analysis data and 77 Se NMR spectrum from being obtained.…”

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confidence: 99%

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Copper(i) diselenocarbamate clusters: synthesis, structures and single-source precursors for Cu and Se composite materials

Dhayal

Liao²,

Hou³

et al. 2015

Dalton Trans.

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Neutral tetrahedral [Cu4(Se2CNnPr2)4] (1), monocationic hydride-centered tetracapped tetrahedral [Cu8(H){Se2CNR2}6]+ (R = nPr, 2H; Et, 3H) and neutral hydride-centered tricapped tetrahedral [Cu7(H){Se2CNR2}6] (R = nPr, 4H; Et, 5H) clusters were formed. They are the first Cu(I) complexes supported by dialkyl diselenocarbamates. The as-synthesized complexes 2H and 3H, formed from a reaction mixture of Cu(I) salts, diselenocarbamates, and [BH4]− in an 8:6:1 ratio, can be further reduced to 4H and 5H, respectively, in the presence of one equiv. of [BH4]−. Replacement of [BH4]− with [BD4]− afforded the deuteride analogues [Cu8(D){Se2CNR2}6]+ (R = nPr, 2D; Et, 3D) and [Cu7(D){Se2CNR2}6] (R = nPr, 4D; Et, 5D), which confirm the presence of hydride in the corresponding (2H, 3H, 4H and 5H) compounds. These complexes were fully characterized by elemental analysis, ESI-MS, and 1H, 2H and 77Se NMR spectroscopy, and their molecular structures were unequivocally established by single crystal X-ray crystallographic analyses (1, 2H–5H). The hydride-encapsulated copper frameworks of (2H, 3H) and (4H, 5H) reveal a tetracapped tetrahedral cage of Cu8 and a tricapped tetrahedral cage of Cu7, respectively, which are enclosed within a Se12 icosahedron constituted by six dialkyl diselenocarbamate ligands. Compounds 2H and 3H display orange emission in both the solid and solution state under UV irradiation at 77 K. In addition, the thermolysis behaviors of 2H were studied to demonstrate the potential of these compounds as single-source precursors for copper selenide nanocomposites, which were analyzed by XRD, EDX, and SEM techniques.

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“…Since then, other small [Cu x ] species (x = 4-8) have been isolated and studied. [12][13][14][15][16][17][18][19][20] In some cases, [Cu x ] structures can be described in terms of sequential addition of a face-capping copper atom to a central Cu 4 -tetrahedron (Figure 1), with interatomic copper distances (d Cu-Cu ) ranging from 2.3-2.8 Å (sum of Cu-Cu van der Waals radii = 2.80 Å). 21 Tetrameric units of the form Cu 4 L 4 are found in both planar 2-dimensional arrays and 3dimensional cubanes (e.g L = N=PR 3 , R = Et, Ph, NMe 3 ).…”

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Isolation of an unusual [Cu₆] nanocluster through sequential addition of copper(i) to a polynucleating ligand

et al. 2017

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Facile Self‐Assembly Synthesis and Characterization of Diselenophosphinato Octanuclear Cu^I Clusters Inscribed in a Twelve‐Vertex Selenium Polyhedron

Cited by 30 publications

References 32 publications

The Formation Mechanism of Binary Semiconductor Nanomaterials: Shared by Single‐Source and Dual‐Source Precursor Approaches

The Formation Mechanism of Binary Semiconductor Nanomaterials: Shared by Single‐Source and Dual‐Source Precursor Approaches

Copper(i) diselenocarbamate clusters: synthesis, structures and single-source precursors for Cu and Se composite materials

Isolation of an unusual [Cu₆] nanocluster through sequential addition of copper(i) to a polynucleating ligand

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Facile Self‐Assembly Synthesis and Characterization of Diselenophosphinato Octanuclear CuI Clusters Inscribed in a Twelve‐Vertex Selenium Polyhedron

Cited by 30 publications

References 32 publications

The Formation Mechanism of Binary Semiconductor Nanomaterials: Shared by Single‐Source and Dual‐Source Precursor Approaches

The Formation Mechanism of Binary Semiconductor Nanomaterials: Shared by Single‐Source and Dual‐Source Precursor Approaches

Copper(i) diselenocarbamate clusters: synthesis, structures and single-source precursors for Cu and Se composite materials

Isolation of an unusual [Cu6] nanocluster through sequential addition of copper(i) to a polynucleating ligand

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Facile Self‐Assembly Synthesis and Characterization of Diselenophosphinato Octanuclear Cu^I Clusters Inscribed in a Twelve‐Vertex Selenium Polyhedron

Isolation of an unusual [Cu₆] nanocluster through sequential addition of copper(i) to a polynucleating ligand